EP0024526A2 - Epoxy based synthetic solder - Google Patents
Epoxy based synthetic solder Download PDFInfo
- Publication number
- EP0024526A2 EP0024526A2 EP80104085A EP80104085A EP0024526A2 EP 0024526 A2 EP0024526 A2 EP 0024526A2 EP 80104085 A EP80104085 A EP 80104085A EP 80104085 A EP80104085 A EP 80104085A EP 0024526 A2 EP0024526 A2 EP 0024526A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- solder
- parts
- weight
- present
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 29
- 239000004593 Epoxy Substances 0.000 title claims abstract description 10
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 20
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 10
- YBBLOADPFWKNGS-UHFFFAOYSA-N 1,1-dimethylurea Chemical compound CN(C)C(N)=O YBBLOADPFWKNGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- PESXPUCWMKUMSI-UHFFFAOYSA-N 3-[2-(dimethylcarbamoylamino)phenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=CC=C1NC(=O)N(C)C PESXPUCWMKUMSI-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000010425 asbestos Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 229910052895 riebeckite Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 12
- 238000009472 formulation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- -1 cycloaliphatic Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- LJBWJFWNFUKAGS-UHFFFAOYSA-N 2-[bis(2-hydroxyphenyl)methyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LJBWJFWNFUKAGS-UHFFFAOYSA-N 0.000 description 1
- KDQTUCKOAOGTLT-UHFFFAOYSA-N 3-[3-(dimethylcarbamoylamino)-4-methylphenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=C(C)C(NC(=O)N(C)C)=C1 KDQTUCKOAOGTLT-UHFFFAOYSA-N 0.000 description 1
- SMGPKUIDJQMBPE-UHFFFAOYSA-N 3-[4-(dimethylcarbamoylamino)phenyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=C(NC(=O)N(C)C)C=C1 SMGPKUIDJQMBPE-UHFFFAOYSA-N 0.000 description 1
- DGRGLKZMKWPMOH-UHFFFAOYSA-N 4-methylbenzene-1,2-diamine Chemical compound CC1=CC=C(N)C(N)=C1 DGRGLKZMKWPMOH-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BQSKIKUCXRZVMV-UHFFFAOYSA-N [2-(carbamoylamino)phenyl]urea Chemical compound NC(=O)NC1=CC=CC=C1NC(N)=O BQSKIKUCXRZVMV-UHFFFAOYSA-N 0.000 description 1
- DPRNGQDPBFKLCK-UHFFFAOYSA-N [4-(carbamoylamino)phenyl]urea Chemical class NC(=O)NC1=CC=C(NC(N)=O)C=C1 DPRNGQDPBFKLCK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- DGJMPUGMZIKDRO-UHFFFAOYSA-N cyanoacetamide Chemical compound NC(=O)CC#N DGJMPUGMZIKDRO-UHFFFAOYSA-N 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- BYTFESSQUGDMQQ-UHFFFAOYSA-N octadecanehydrazide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NN BYTFESSQUGDMQQ-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/54—Inorganic substances
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/919—Metal patching composition, e.g. body solder
Definitions
- This invention is directed to a synthetic solder based upon epoxy resins and a specific curing system of a combination of 1,1'-o-phenylenebis(3,3-dimethylurea) wherein the phenyl moiety is optionally substituted with up to two alkyl (C l-3 ) groups and dicyandiamide.
- Solders have been known for a long time and lead solder in particular has found wide application in automotive manufacturing.
- the Environmental Protection Agency has restricted the use of such lead solders after 1980 and therefore there is a need for a suitable product to replace it. Accordingly much research has been conducted to produce a rapidly curing synthetic product which will be satisfactory for use on assembly lines in automotive plants.
- U.S. Patent 3,386,955 discloses that various phenylenebis(3,3-dimethylureas) are useful latent epoxy curing agents.
- Example 5 discloses the use of a mixture of o-, m-, and p-phenylenebis(3,3-dimethylureas) to cure an epoxy resin.
- U.S. Patent 3,386,956 discloses that methyl substituted phenylenebisureas may be combined with a co- curing agent selected from dicyandiamide, stearic hydrazide, succinimide and cyanoacetamide to cure epoxy resins.
- the polyepoxides used in making the solder have a plurality of reactive 1,2-epoxy groups. They may be polymeric or monomeric (though preferably polymeric), saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and they may be substituted if desired with other substituents besides the epoxy groups, e.g. hydroxyl groups, ether radicals, halogen atoms, and the like.
- Suitable polyepoxides are such as are disclosed in U.S. Patent 3,386,956, incorporated herein by reference.
- Preferred polyepoxides useful herein are those ---prepared from (1) polyhydric-phenols such as 4,4'-dihydroxy- dihydroxydiphenylmethane, 3,3'-dihydroxydiphenyldiethyl- methane, 3,4'-dihydroxydiphenylmethylpropylmethane, 2,3'-dihydroxydiphenylethylphenylmethane, 4.4'-dihydroxydiphenyl- propylphenylmethane, 4,4'dihydroxydiphenylbutylphenylmethane, 2,2'-dihydroxydiphenylditolylmethane, 4,4'-dihydroxydiphenyl- tolylmethylmethane, and the like, and an epihalohydrin such as epichlorohydrin; (2) an epoxy novolac resin obtained by reacting, preferably in the presence of a basic catalyst, an epihalohydrin such as epichlorohydrin with the resinous condensate of an al
- the polyepoxide may be rubber modified to increase the strength and toughness properties of the solder.
- the l,l'-o-phenylenebis(3,3-dimethylurea) may be prepared by reacting o-phenylene diisocyanate and dimethylamine in the manner of Example 5 of U.S. Patent 3,386,966 incorporated herein by reference, or more preferably by reacting o-phenylenediamine with dimethylcarbamyl chloride in the presence of an HC1 acceptor.
- the substituted phenyl kompounds may be prepared in like manner.
- the fillers used herein to reinforce the solder may be any conventional filler which is compatible with the polyepoxide and suitable for use in solders.
- these fillers include aluminum powder, calcium carbonate, wood flour, metal oxides like iron oxide, gypsum, asbestos, talc, clays, and other silicates and the like. Asbestos is not preferred due to environmental problems.
- the filler may be treated with such as stearic acid to improve the thixotropic properties of the composition.
- the fillers have particle sizes on the order of 1-30 microns.
- epoxide additives such as thixotropic agents, dyes, pigments, flame retarding agents, as well as other compatible natural and synthetic resins can also be added into the composition.
- the l,l'-o-phenylenebis(3,3-dimethylurea) compound and the dicyandiamide are used in effective curing amounts.
- the bisurea is generally used in amounts of about 1 to 10 parts by weight and the dicyandiamide in amounts of about 2 to 20 parts by weight, both per 100 parts by weight of polyepoxide resin.
- the fillers are generally present in total amounts of about 100 to 300 parts by weight per 100 parts by weight of polyepoxide resin.
- the solder contains about 1.5 to 4 part: by weight 1,1'-o-phenylenebis(3,3-dimethylurea), about 4 to 10 parts by weight dicyandiamide, and about 150 to 225 parts by weight filler, all per 100 parts by weight of polyepoxide resin.
- a second formulation is prepared as in Example I, with the exception that 2 parts of 1,1'-(2,4-tolylene)-bis-(dimethylurea) is used in place of the o-phenylene compound.
- Lap shear tests in accordance with A.S.T.M. Test D100Z are conducted with each of the formulations of Examples I and II using shimmed, grit blasted, 40 mil thick steel and curing the samples for 5 minutes at 200°C. in a hydraulic press.
- the samples using the formulation of Example I yield an average lap shear of 3200 psi whereas those of Example II are only 2550 psi and exhibit porous glue lines.
- Example 1 The procedure of Example 1 is twice repeated with.2 and 4 parts of 1,1'-p-phenylenebis(3,3-dimethylurea) used in place of the o-phenylene compound of the present invention. Upon exposure to the same curing conditions as in Example I, the solders do not cure and remain only partially hardened after cooling.
- the composition is applied to a mold and cured for 5 minutes at 200°C.
- the resultant samples are smooth and uniform.
- the samples are tested for flexural strength in accordance with A.S.T.M. Test D 790 and found to have a flexural strength to rupture of 11,500 psi at room temperature, and of 10,500 psi at 100°C.
- 3,4-diaminotoluene is reacted with excess N,N-dimethylcarbamyl chloride in the presence of slurried calcium carbonate to yield 1,1'-(3,4-toylene)bis(3,3-dimethylurea) which has a melting point of 145-146°C.
- Example I The procedure of Example I is repeating using the tolylene bisurea in place of the phenylenebisurea and the composition cures within 5 minutes to yield a smooth, dense epoxy patch filling the recess in the desired manner.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Epoxy based synthetic solders are prepared from (a) at least one epoxy resin, (b) at least one filler, (c) 1,1'-0-phenylenebis- (3,3-dimethylurea) wherein the phenyl moiety is optionally substituted with up to two alkyl (C1-3) groups and (d) dicyandiamide.
Description
- This invention is directed to a synthetic solder based upon epoxy resins and a specific curing system of a combination of 1,1'-o-phenylenebis(3,3-dimethylurea) wherein the phenyl moiety is optionally substituted with up to two alkyl (Cl-3) groups and dicyandiamide.
- Solders have been known for a long time and lead solder in particular has found wide application in automotive manufacturing. The Environmental Protection Agency has restricted the use of such lead solders after 1980 and therefore there is a need for a suitable product to replace it. Accordingly much research has been conducted to produce a rapidly curing synthetic product which will be satisfactory for use on assembly lines in automotive plants.
- U.S. Patent 3,386,955 discloses that various phenylenebis(3,3-dimethylureas) are useful latent epoxy curing agents. Example 5 discloses the use of a mixture of o-, m-, and p-phenylenebis(3,3-dimethylureas) to cure an epoxy resin.
- U.S. Patent 3,386,956 discloses that methyl substituted phenylenebisureas may be combined with a co- curing agent selected from dicyandiamide, stearic hydrazide, succinimide and cyanoacetamide to cure epoxy resins.
- It has now unexpectedly been discovered that l,l'-o-phenylenebis(3,3-dimethylurea) wherein the phenyl moiety is optionally substituted with up to two alkyl (CI-3) groups when combined with dicyandiamide will produce a curing system for epoxy resins which results in an unexpectedly superior solder in that it provides a very rapid cure (about 3-5 minutes at about 200-225°C) for the relatively large masses of filled epoxy solder which will be used on an automotive assembly line, while achieving an essentially smooth, voidfree, sandable surface prior to paint finishing. The m-and p- phenylenebisurea compounds do not produce such a solder. They, as well as other bisurea compounds either do not produce a satisfactory cure to achieve a hard sandable surface, or do cause severe exothermic effects which yield a porous or cracked solder that is not suitable for painting to a glossy finish. Other well known epoxy curing agents are environmentally unstable or undesirable in that toxic products are released during curing.
- The polyepoxides used in making the solder have a plurality of reactive 1,2-epoxy groups. They may be polymeric or monomeric (though preferably polymeric), saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic, and they may be substituted if desired with other substituents besides the epoxy groups, e.g. hydroxyl groups, ether radicals, halogen atoms, and the like.
- Suitable polyepoxides are such as are disclosed in U.S. Patent 3,386,956, incorporated herein by reference.
- Preferred polyepoxides useful herein are those ---prepared from (1) polyhydric-phenols such as 4,4'-dihydroxy- dihydroxydiphenylmethane, 3,3'-dihydroxydiphenyldiethyl- methane, 3,4'-dihydroxydiphenylmethylpropylmethane, 2,3'-dihydroxydiphenylethylphenylmethane, 4.4'-dihydroxydiphenyl- propylphenylmethane, 4,4'dihydroxydiphenylbutylphenylmethane, 2,2'-dihydroxydiphenylditolylmethane, 4,4'-dihydroxydiphenyl- tolylmethylmethane, and the like, and an epihalohydrin such as epichlorohydrin; (2) an epoxy novolac resin obtained by reacting, preferably in the presence of a basic catalyst, an epihalohydrin such as epichlorohydrin with the resinous condensate of an aldehyde, e.g., formaldehyde, and either a monohydric phenol or a polyhydric phenol; and (3) tris-(hydroxyphenyl)methane based epoxide resins.
- Optionally the polyepoxide may be rubber modified to increase the strength and toughness properties of the solder.
- The l,l'-o-phenylenebis(3,3-dimethylurea) may be prepared by reacting o-phenylene diisocyanate and dimethylamine in the manner of Example 5 of U.S. Patent 3,386,966 incorporated herein by reference, or more preferably by reacting o-phenylenediamine with dimethylcarbamyl chloride in the presence of an HC1 acceptor. The substituted phenyl kompounds may be prepared in like manner.
- The fillers used herein to reinforce the solder may be any conventional filler which is compatible with the polyepoxide and suitable for use in solders. Examples of these fillers include aluminum powder, calcium carbonate, wood flour, metal oxides like iron oxide, gypsum, asbestos, talc, clays, and other silicates and the like. Asbestos is not preferred due to environmental problems. Optionally the filler may be treated with such as stearic acid to improve the thixotropic properties of the composition. Generally the fillers have particle sizes on the order of 1-30 microns.
- 'Additionally conventional epoxide additives such as thixotropic agents, dyes, pigments, flame retarding agents, as well as other compatible natural and synthetic resins can also be added into the composition.
- In the solder compositions of the present invention, the l,l'-o-phenylenebis(3,3-dimethylurea) compound and the dicyandiamide are used in effective curing amounts. The bisurea is generally used in amounts of about 1 to 10 parts by weight and the dicyandiamide in amounts of about 2 to 20 parts by weight, both per 100 parts by weight of polyepoxide resin. The fillers are generally present in total amounts of about 100 to 300 parts by weight per 100 parts by weight of polyepoxide resin.
- Preferably, the solder contains about 1.5 to 4 part: by weight 1,1'-o-phenylenebis(3,3-dimethylurea), about 4 to 10 parts by weight dicyandiamide, and about 150 to 225 parts by weight filler, all per 100 parts by weight of polyepoxide resin.
- The following non-limiting examples are presented to illustrate the present invention and its benefits in producing solders which are satisfactory for assembly line applications in automotive plants in that they produce the characteristics described above and, in addition, (1) produce a dense, uniform patch while having a controlled exotherm which precludes foaming or charring of the epoxy resin and (2) pass thermal cycling tests in simulated application studies. All parts and percents are by weight unless otherwise specified.
- In a vacuum equipped planetary mixer the following ingredients are blended to achieve an air-free thixotropic mixture:
- Six ounces of the above formulation is applied to the recess of an indented panel of steel for testing. The sample is cured for 3 minutes at 70°C. under an infrared heater. The solder reaches a maximum temperature of 200°C.
- After cooling to room temperature the sample is sanded to yield a smooth dense, epoxy patch filling the recess in the desired manner.
- A second formulation is prepared as in Example I, with the exception that 2 parts of 1,1'-(2,4-tolylene)-bis-(dimethylurea) is used in place of the o-phenylene compound.
- When subjected to the same cure cycle the sample smokes and foams. Sanding of the sample produces an unsatisfactory, porous surface.
- Lap shear tests in accordance with A.S.T.M. Test D100Z are conducted with each of the formulations of Examples I and II using shimmed, grit blasted, 40 mil thick steel and curing the samples for 5 minutes at 200°C. in a hydraulic press. The samples using the formulation of Example I yield an average lap shear of 3200 psi whereas those of Example II are only 2550 psi and exhibit porous glue lines.
- The procedure of Example 1 is twice repeated with.2 and 4 parts of 1,1'-p-phenylenebis(3,3-dimethylurea) used in place of the o-phenylene compound of the present invention. Upon exposure to the same curing conditions as in Example I, the solders do not cure and remain only partially hardened after cooling.
- The following formulation is prepared as in Example I:
- The composition is applied to a mold and cured for 5 minutes at 200°C. The resultant samples are smooth and uniform. The samples are tested for flexural strength in accordance with A.S.T.M. Test D 790 and found to have a flexural strength to rupture of 11,500 psi at room temperature, and of 10,500 psi at 100°C.
- 3,4-diaminotoluene is reacted with excess N,N-dimethylcarbamyl chloride in the presence of slurried calcium carbonate to yield 1,1'-(3,4-toylene)bis(3,3-dimethylurea) which has a melting point of 145-146°C.
- The procedure of Example I is repeating using the tolylene bisurea in place of the phenylenebisurea and the composition cures within 5 minutes to yield a smooth, dense epoxy patch filling the recess in the desired manner.
Claims (10)
1. An epoxy based synthetic solder comprising at least one epoxy resin having a plurality of 1,2-epoxy groups, at least one filler, and an effective curing amount of 1,1'-o-phenylenebis(3,3-dimethylurea) wherein the phenyl moiety is optionally substituted with up to two alkyl (Cl-3) groups and dicyandiamide.
2. The solder of Claim 1 wherein the phenyl moiety is unsubstituted.
3. The solder of Claim 1 wherein the phenyl moiety is substituted with one methyl group meta to either urea moiety.
4. The solder of Claim 2 wherein at least one epoxy resin is prepared from a polyhydric phenol and an epihalohydrin.
5. The solder of Claim 4 wherein the polyhydric phenol is 4,4'-dihydroxyddiphenyldimethylmethane and the epihalohydrin is epichlorohydrin.
6. The solder of Claims 2 and 3 wherein at least one epoxy resin is an epoxy novolac resin.
7. The solder of Claims 2 and 3 wherein the fillers are selected from aluminum powder, calcium carbonate, wood flour, gypsum, talc, asbestos, metal oxides and clays.
8. The solder of Claims 2, 3, and 5 wherein the i,l'-o-phenylenebis(3,3-dimethylurea) is present in about 1 to 10 parts by weight, the dicyandiamide is present in about 2 to 20 parts by weight, and the filler is present in about 100 to 300 parts by weight, all per 100 parts by weight of total epoxy resin.
9. The solder of Claims 2, 3, and 5 wherein the l,l'-o-phenylenebis(3,3-dimethylurea) is present in about 1.5 to 4 parts by weight, the dicyandiamide is present in about 4 to 10 parts by weight, and the filler is present in about 150 to 225 parts by weight, all per 100 parts of total epoxy resin.
10. The cured solder of Claims 1, 2 and 3.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7094879A | 1979-08-30 | 1979-08-30 | |
| US145300 | 1980-05-01 | ||
| US06/145,300 US4273686A (en) | 1979-08-30 | 1980-05-01 | Epoxy based synthetic solder |
| US70948 | 1998-05-01 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0024526A2 true EP0024526A2 (en) | 1981-03-11 |
| EP0024526A3 EP0024526A3 (en) | 1981-03-25 |
| EP0024526B1 EP0024526B1 (en) | 1984-06-13 |
Family
ID=26751661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80104085A Expired EP0024526B1 (en) | 1979-08-30 | 1980-07-15 | Epoxy based synthetic solder |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4273686A (en) |
| EP (1) | EP0024526B1 (en) |
| AR (1) | AR226067A1 (en) |
| BR (1) | BR8005122A (en) |
| CA (1) | CA1157187A (en) |
| DE (1) | DE3068186D1 (en) |
| ES (1) | ES494615A0 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0138209A3 (en) * | 1983-10-14 | 1986-09-17 | Hitachi, Ltd. | Epoxy resin composition |
| EP0481228A3 (en) * | 1990-10-17 | 1992-09-02 | American Cyanamid Company | Induction curing electro-coatable seam filler |
| EP0551063A1 (en) * | 1992-01-07 | 1993-07-14 | Fina Research S.A. | Use of protective coating compositions for underbody coatings |
| US6565772B2 (en) | 2001-09-25 | 2003-05-20 | Midwest Thermal Spray | Conductive resin composition |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383060A (en) * | 1982-06-01 | 1983-05-10 | General Motors Corporation | Epoxy adhesive for structurally bonding molded SMC |
| GB2300187B (en) * | 1995-04-28 | 1998-09-02 | Hodogaya Chemical Co Ltd | Cure-accelerator for epoxy resin |
| US5851311A (en) * | 1996-03-29 | 1998-12-22 | Sophia Systems Co., Ltd. | Polymerizable flux composition for encapsulating the solder in situ |
| US8076395B2 (en) * | 2009-09-11 | 2011-12-13 | Air Products And Chemicals, Inc. | Low temperature curable epoxy compositions containing urea curatives |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3386955A (en) * | 1966-01-14 | 1968-06-04 | American Cyanamid Co | Substituted ureas as low temperature epoxy curing agents |
| GB1293142A (en) * | 1969-09-09 | 1972-10-18 | Ciba Geigy Uk Ltd | Curable epoxide resin compositions |
| US3660316A (en) * | 1970-11-20 | 1972-05-02 | American Cyanamid Co | Polyepoxide bisurea adhesive composition containing a 1 - cyano - 3-(lower alkyl) guanidine as auxiliary curing agent |
| GB1399800A (en) * | 1973-02-09 | 1975-07-02 | Lockheed Aircraft Corp | Corrosion preventive metal bond/weldbond adhesive |
-
1980
- 1980-05-01 US US06/145,300 patent/US4273686A/en not_active Expired - Lifetime
- 1980-07-15 CA CA000356250A patent/CA1157187A/en not_active Expired
- 1980-07-15 EP EP80104085A patent/EP0024526B1/en not_active Expired
- 1980-07-15 DE DE8080104085T patent/DE3068186D1/en not_active Expired
- 1980-08-01 AR AR282024A patent/AR226067A1/en active
- 1980-08-14 BR BR8005122A patent/BR8005122A/en unknown
- 1980-08-29 ES ES494615A patent/ES494615A0/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0138209A3 (en) * | 1983-10-14 | 1986-09-17 | Hitachi, Ltd. | Epoxy resin composition |
| EP0481228A3 (en) * | 1990-10-17 | 1992-09-02 | American Cyanamid Company | Induction curing electro-coatable seam filler |
| EP0551063A1 (en) * | 1992-01-07 | 1993-07-14 | Fina Research S.A. | Use of protective coating compositions for underbody coatings |
| US6565772B2 (en) | 2001-09-25 | 2003-05-20 | Midwest Thermal Spray | Conductive resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0024526B1 (en) | 1984-06-13 |
| CA1157187A (en) | 1983-11-15 |
| ES8105761A1 (en) | 1981-07-01 |
| ES494615A0 (en) | 1981-07-01 |
| BR8005122A (en) | 1981-03-04 |
| DE3068186D1 (en) | 1984-07-19 |
| EP0024526A3 (en) | 1981-03-25 |
| AR226067A1 (en) | 1982-05-31 |
| US4273686A (en) | 1981-06-16 |
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